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Restricted substances in leather

>> TFL Eco Guidelines – Your guide through the maze of RSL lists

PTT F L P R OT E C

LST F L LO W S U L F I D E T E C

CTT F L C O O L T E C

DWT F L D R Y W A L K T E C

WLT F L W H I T E L I N E T E C

MTT F L M A X I T E C

ETT F L E C O T E C

1TFL – Great chemicals. Excellent advice.

TFL Eco Guidelines

Information on Restricted Substances

Test Methods and specifications

, Choosing the right test methods 13

, Testing formaldehyde

, Testing heavy metals

, VOC emission testing

, Who develops test methods? 14

, How are detection limits set?

, What are natural environmental limits?

Restricted Substances relevant to 16–24

Leather Manufacture

Detailed discussion

, Glossary 25

Is leather a safe product? 26

>> Contents

Restricted Substances list

A multitude of regulations on

chemical substances

, National regulations 5

, International agreements and regulations 7

, Eco Labels for consumer items

, ZDHC MRSL Lists 8

, RSL List form manufacturers and brands 9

Chemical substances of concern in 9

leather manufacture

How to comply with the various RSL? 10

2

TFL Eco Guidelines

This publication is the latest update of our volume

on Restricted Substances and is part of a series

that TFL is preparing in order to enhance the un-

derstanding of environmental and ecological as-

pects in leather manufacturing. Worldwide there

is increasing emphasis on operating in a manner

that is compatible with the best ecological and

environmental practices. This requires many

tanneries and supply industries to have a better

understanding of the whole ecological process of

leather manufacturing from start to finish.

Chemicals, whether from synthetic or natural

origin, play a significant role in the the tanning

industry since they end up either in the final

leather and potentially also in wastewater, sludge,

by products and gaseous emissions. There is

increasing pressure to use chemicals which do not

harm the consumer and the environment and to

apply them in a responsible manner using clean

technology practices. Tanneries must comply

with a rapidly increasing set of regulations and

commercial specifications, which restrict the use

of chemical substances considered to have

hazardous or toxic properties.

So it is logical that for the leather industry a good

understanding of restricted substances is required

today. This publication presents the topic in a

clear and easy to understand manner for staff

working in tanneries and the leather industry.

>> Introduction

2 3

>> Restricted Substance List has become a common term in the tanning industry.

4

TFL Eco Guidelines – Restricted Substances Lists (RLS)

“Restricted Substance List”, or its commonly

used abbreviation “RSL”, has become a common

term in the tanning industry.

It is important to distinguish between a

, Product Restricted Substance List

(often called PRSL) which restricts the use of

chemicals in the final product (i.e. leather) and

, Material Restricted Substance Lists

(i.e. MRSL issued by ZDHC) which addresses

restricted chemicals in the chemical product

used for making leather.

The first question that immediately arises is:

Who sets the requirements in the RSL lists that

are on the desk in the tannery office?

Basically there are 2 groups involved:

1. Legislators

, National regulations and laws

, International agreements and regulations

2. Manufacturers/Brands, Ecolabels,

NGO’s and consortiums (such as ZDHC)

, Ecolabels for consumer items

, Restricted Substance Lists (RSL) for consumer

products like leather

, Restricted Substance Lists for chemical

products (i.e. MRSL issued by ZDHC)

National regulations and lawsEach country has its own regulations and laws

regarding chemicals. If we look at restricted

chemical substances on a global basis, it is clear

that some countries have considerably more

regulations in this area than others.

REACH

Worldwide the strictest regulations for chemicals

are those in the European Union (EU) countries,

where all the many previous chemical EU

Directives have been put together into one Annex

(Annex XVII) of the EU Regulation 1907/2006,

commonly called REACH. This regulation is

mandatory for all 26 EU countries.

The EU-REACH Regulation

(and the former EU Directives) restricts either:

, The sale or manufacture within the EU of

product formulations containing more than

certain amounts of chemical substances or

, The presence of certain chemical substances

in consumer goods.

A multitude of regulations>> National regulations and laws

4 5


What does REACH mean for

the European tanner?

The European tanner purchasing a chemical from

a European supplier will be required to disclose to

the chemical supplier the use of such chemical to

ensure that a valid, risk based exposure scenario

for the identified use can be established. The

REACH registration of a chemical substance and

the considerable costs associated with it are the

responsibility of the EU chemical manufacturer

or importer of the chemical. Only if the tanners

are themselves importing chemicals into the EU,

they will be directly involved in the registration

process.

What does REACH mean for

the non-European tanner?

Tanners in other parts of the world will not need

to undertake any registration process but will

need to be careful with the selection of their

chemical products. If their leather will be export-

ed at some stage to European customers, the

leather must comply with REACH restricted sub-

stance requirements for consumer items, as given

in Annex XVII of the EU Regulation. In addition,

the Substances of High Concern (SVHC), as listed

in Annex XIV (REACH), must not be present in the

leather at more than 0.1 % (= 1000 ppm).

Other countries are planning or have already

started to implement similar chemical regulations

to the REACH Regulation for the EU countries. The

hope is that there will not be significant variations

between countries in terms of the legislation.

Harmonisation of the requirements would be an

advantage to all, but this is not yet the case.

In the USA the Federal Agencies, EPA (Environ-

mental Protection Agency) and CPSC (Consumer

Product Safety Commission) control regulations

and guidelines at a national level. In addition, the

individual states have their own regulations. For

example, the state of California has its “Proposi-

tion 65” regulation, which protects Californian

citizens from exposure to certain harmful sub-

stances whose presence has to be listed on con-

sumer items with appropriate warning phrases.

Japan has regulations for harmful substances;

the most commonly seen in the leather industry

is the Law 112 restricting harmful substances

(e.g. formaldehyde) in household products.

China has national standards, for example:

GB 18401 and GB 20400, which limit the amount

of harmful substances in consumer items.

Regulations in one area can very quickly have an

impact on a global basis, this is typical of a num-

ber of EU restrictions. Many leather articles made

in other parts of the world end up being sold in

the EU countries or in countries which exercise

similar chemical regulatory practices. A good

example is the forbidden aromatic amines from

azo dyes or PCP (Penta Chloro Phenol), where the

initial EU Directive quickly became the require-

ment worldwide.

6

Behind each Eco- label stands mostly a test institute or a group of test institutes.

International agreements and regulationsThere are several international treaties and agree-

ments administered by the United Nations which

limit specific chemicals. Two examples of these

international treaties are:

The “Montreal Protocol on Substances that

Deplete the Ozone Layer”, designed to globally

phase out the use of substances that can cause a

reduction in the ozone layer. The Montreal Proto-

col has been ratified by 196 nations and requires

countries to implement their own legislation.

For example, the EU implemented Regulation

1005/2009 that lists and controls the use of all

the ozone depleting substances in EU countries.

The “Stockholm Convention on Persistent

Organic Pollutants (POPs)” is signed by 151

countries. It requires the parties involved to take

measures to eliminate or reduce the release

of POPs into the environment. Initially 12 POP

substances were identified and in May 2009

an additional 9 substances were added. These

substances are chlorinated organic pesticides,

brominated organic flame retardants and perfluo-

roctane sulfonates (PFOS).

Ecolabels for consumer itemsThere are an increasing number of Ecolabels

available. To be successful, the Ecolabel needs

to be recognised and to be used with consumer

items. In most cases, behind each Ecolabel is a

test institute or a group of test institutes, who are

responsible for monitoring the compliance and

issuing of the Ecolabels. In Europe, the promot-

ing, marketing and testing for Ecolabels are now

a considerable commercial business for those

test houses involved and some brands link their

products to an Ecolabel.

, Ecolabels and brands are usually the first

to react to “chemical dangers”, which are pub-

lished in media reports and by pressure groups

, Usually the Ecolabels are ahead of any

legislation on the topic

, Most have established their own “restricted

substance” specifications and these are often

mistakenly interpreted by tanners to be official

regulations for Europe

Some typical examples of Ecolabels seen in

European shops on clothes and leather articles

are: Oeko-Tex 100, SG Label, Blue Angel issued

by the German Government for Environment, PFI

Label, etc. These labels inform the customer that

the consumer article has been tested for harmful

substances and is in compliance with the specifi-

cations of that particular Ecolabel.

Note: Many Ecolabels are strongly textile

oriented and, for example, restrict the total

chromium (Cr) to very low values, which makes

it effectively impossible that chrome-tanned

leather articles can comply.

6 7


The MRSLList by ZDHC:

The MRSL issued by

ZDHC can be seen

as an important

approach consolidat-

ing valuable RSL data

into one managebale

list of restricted

chemicals.

EU Footwear Ecolabel

The EU Footwear Ecolabel has been developed

to use the “EU flower” Ecolabel for footwear

that comply with restricted substances in the

shoe and packaging, as well as complying with

ecological requirements during the various

material and shoe manufacturing operations and

during its use. The aims of this Ecolabel are well

intended but without a commercial organisation

promoting and marketing it, like other successful

Ecolabels, it will be difficult to get acceptance by

the footwear industry.

EU Footwear label addresses the Environmental

impact and life cycle analysis considering:

, Packaging

, Emissions while producing material, especially

leather tanneries (COD criteria for waste water,

Cr recovery, short chain chlorinated paraffins,

forbidden chemicals)

, Energy consumption and product

environmental footprint

, End of life – best use option

, PVC, nitrosamines in rubber

, Durability criteria

Manufacturers, brands, NGO’s ZDHC Programme –

Zero Discharge of Hazardous Chemicals

The ZDHC foundation is a collaboration of Green

Peace with global signatory brands, value chain

affiliates and associates whose goal is the elimina-

tion of hazardous chemicals from the textile and

footwear supply chain. The ZDHC programme is

based on Input Stream Management which means

regulating the use of hazardous chemicals right

from the beginning of the value chain. ZDHC has

established a Material Restricted Subtsance

List (MRSL) not only for textile industry but also

recently for leather chemicals. The MRSL list gives

allowable limits of hazardous substances and the

related testing methods for such chemicals. The

MRSL is based on data from important national

and international regulations and studies but also

on the input from brands and manufacturers. The

MRSL can be seen as an important approach con-

solidating valuable RSL data into one managebale

list of restricted chemicals.

The MRSL list is a living document and currently

does not include biocides and substances like

formaldehyde which are addressed by individual

RSL and regulations.

Global brands

The global brands, some examples are Adidas,

Nike, H&M, Clarks, IKEA, etc., publish their own

lists of restricted substances (RSL) and update

them at regular intervals. The limit values in the

lists are for leather and other materials being

used by these global brands. Many tanners sup-

plying the global brands then use or copy these

lists and pass them on down the supply chain, for

example to their chemical product suppliers, with

the same limits and the same test methods. In

many cases the test methods are specifically for

leather and not suitable for analysing chemicals.

In most cases the global brands base their specifi-

cation limit values on various regulations that al-

ready exist. For example, the limit for nonylphenol

ethoxylate surfactants (NPEO) in leather is often

1000 mg/kg as in the EU Regulation for chemical

formulations but there are brands which set limits

as low as 100mg/kg (100ppm).

When a regulation does not exist, the brands es-

tablish their own limit values. For formaldehyde in

leather, where there is no EU Regulation, the typ-

ical limits in leather with skin contact are 20 mg/

kg for baby shoes and 75 mg/kg (Japan) / 100

mg/kg for adult clothes and shoes. If there is no

skin contact, the formaldehyde limits are typically

8


Global Automotive Declarable Substance List: Despite the fact that RSL product lists contains hundreds of substances only few are of real concern.

around 300 mg/kg. Interestingly the cosmetic in-

dustry allows skin contact items with considerably

higher levels for releasable formaldehyde. Often

allowable limits in RSL lists are not clearly science

or risk based but are a precautionary measure or

result from ‘green’ competition.

Automotive industry

The European automotive industry has to comply

with the End of Life Vehicle Directive require-

ments and has set up a data base to record

each component used in cars. To ensure that

information on restricted substances is collected

worldwide, the Global Automotive Declarable

Substance List (GADSL) has been established

and requires those in the supply chain to provide

information for the listed 139 substances. The

GADSL list is normally updated each year.

In the recent past an increased emphasis is put on

interior car air quality where car seat leather plays

an important role with regards to emissions of

volatile substances, which are hazardous and of

potentially unpleasant odor.

The Japanese Automotive Industry (JAMA) in-

troduced in 2005 voluntary air quality standards

which limit the emissions inside cars. This data

was taken directly from that for emissions inside

houses and corrected for the volume difference;

so it also included some household substances

that are not found inside a car. More important is

that in addition to formaldehyde, for the first time

acetaldehyde was restricted – at a very low level.

(see page 16).

The GB/T 27630-2011 (Guidelines for Air Quali-

ty Assessment of Passenger Vehicles) issued by

the Chinese Ministry of Enviornmental Protection

goes in a similar direction as JAMA but including

further hazardous substances (see page 16)

Chemical substances of concern in leather manufacture RSL lists range from small lists with the key

substances relevant for leather, to very large lists

with many hundreds of different chemical sub-

stances of which only a few are of real concern

for leather. In the following section the most

relevant substances for leather are put togeth-

er (They are reviewed in more detail in section

Restricted Substances) (see page 16)

Legally restricted chemical substances

The following chemical substances are restricted

through legal restrictions:

, Allergenic and sensitising dyes

, Aromatic amines from azo dyes

, Boron containing substances

, Brominated organic flame retardants

, Chlorinated paraffins

(short chain, C10 – C 13, SCCP)

, Chlorinated phenols (PCP, TeCP and TriCP)

, Chromium (VI)

, Dimethyl fumarate

, Heavy metals

, N-methyl pyrrolidone

, Nonylphenol ethoxylate and nonylphenol

, Organotin compounds

, Perfluorooctane sulfonate (PFOS and related

PFOA)

, Phthalates

, Polyaromatic hydrocarbons (PAH)

, Substances of Very High Concern (SVHC)

Chemical substances restricted by Ecolabels,

brands and manufacturers

The following chemical substances can be

restricted by Ecolabels and brands:

, Formaldehyde

, Acetaldehyde (air emission)

, Biocides

, Hazardous volatile organic substances (VOC)

8 9

>> Input stream management

Chemical supplier

Uncritical chemicals Chemicals on RSL list ”Safe“ end product

Tannery Brand

BBSTOP


Difficult problems for tanners: The most promising approach however in this direction is the Material Restricted Substance List for chemical products used for leather manufacture.

How to comply with the various RSL lists?It is a problem for tanners to find their way

through the jungle of regulations and customer

requirements for restricted substances. Many

substances in the long lists have no relevance

for the leather industry; take the example of a

tanner requesting a written statement that there

is no asbestos fibres in the leather chemicals he

is using. Harmonisation of the large numbers

of restricted substance lists would be a very

positive thing for all concerned, but considering

the various interest of all stakeholders it is not

easy to achieve in today’s environment. The most

promising approach however in this direction is

the Material Restricted Substance List for chem-

ical products used for leather manufacture. It

list all chemical substances which should not be

present in a chemical product beyond a given

limit. The MRSL is issued by ZDHC a multistake

holder association where NGO, brands and chem-

ical manufacturers (via the LWG-Leather Working

Group) and other experts working together. The

MRSL list is being updated continuously and rep-

resents state-of-the-art knowledge on restricted

substances. It is an approach which is based on

Input Stream Management which means avoiding

restricted substances right from the beginning of

leather manufacture.

Not included in the MRSL list are biocides and

products like formaldehyde, acetaldehydeand

chromium(VI) which need to be addressed indi-

vidually and be tested for. Apart from these the

ZDHC-MRSL list is likely to cover the rest of the

RSL requirements from brands and manufacturers.

TFL uses the ZDHC–MRSL requirements as a base

for their RSL management policy which also takes

into account other legal requirements.

TFL Product Compliance Policy 1. Regulatory compliance

The chemicals of TFL listed in Annex A of this

declaration:

, Comply with the European Union (EU) regula-

tions 1907/2006 (REACH) and 1272/2008 (CLP

Regulation). As required by these EU Regula-

tions, TFL identifies hazards in Section 2 of the

respective Safety Data Sheet (SDS) and lists

substances classified as hazardous to health or

the environment clearly in Section 3 of the re-

spective SDS. The SDS is the legally prescribed

document regarding safety of individual chemi-

cal products supplied.

, Comply with the REACH requirements for Sub-

stances of Very High Concern (SVHC) in REACH

Annex XIV (authorisation) and in the Candidate

List for SVHC (according to art. 59.1 of REACH).

10


TFL products listed in Annex A are in compli-

ance with the SVHC and SVHC candidate list,

including its concentration limit requirements.

The SVHC candidate substance list is updated

every 6 months and available at:

http://echa.europa.eu/candidate-list-table

, Comply with the restricted substance require-

ments of REACH Annex XVII REACH Annex XVII

contains the EU restrictions for the manufac-

ture, marketing and use of chemical substanc-

es, and is available at:

http://echa.europa.eu/addressing-

chemicals-of-concern/restrictions/substanc-

es-restricted-under-reach

, Comply with EU Biocide Regulation

528/2012TFL leather chemicals comply with EU

regulation 528/2012 concerning the sale and

use of biocidal products. The text of the

regulation is available at:

https://echa.europa.eu/regulations/biocid-

al-products-regulation/legislation

2. Compliance with the requirements of the

Manufacturing Restricted Substances List

(MRSL) of ZDHC (Version 1.1, December 2015)

TFL has issued a separate Product Compliance

Statement which is updated regularly and which

applies to all TFL products. In a special Annex it

also lists the (trace) level amounts of formalde-

hyde, phenol and metals contained in some TFL

products. It also listss biocide actives TFL is using

and which all comply with EU Biocide Product

Directive (BPD). Such a Product Complaince State-

ment is a living document since the substance

lists are continually being updated. Many of them

derive from REACH where Substances of Very

High Concern are identified on a risk and science

based analysis and put onto the SVHC list (see

page 6).

Based on practical tests and experience TFL

believes that by using their products in a correct

way it is possible to make leather which is

safe to the consumer and the environment

and which satisfies all major RSL requiremenst in

the industry.

Verification of a chemical

supplier’s conformance

It is the right of a leather manufacturer to know

how trustworthy a RSL statement issued by a

chemical supplier really is. If he can rely on a

chemcials suppliers statement he will be able to

eliminate a lot of (unnecessary) testing of his final

product and focus on substances which can be

formed or reduced during manufacture

(e.g. Cr(VI), formaldehyde, acetaldehyde).

In the textile chemical industry audit and certi-

fication systems for chemical suppliers already

exist (i.e. BlueSign, GOTS, OekoTex Eco Passpart).

For the leather chemical industry discussions are

on the way to develop something similar.

For the time being, however, chemical suppliers

are doing self assessments based on internal

audits etc.

TFL has established an internal system which

consists of own chemical testing and chemical

testing of raw material (chemical substance)

suppliers. TFL will align with an external audit and

certification system as soon as an appropriate

one is in place.

It is very clear that chemical substances need

proper and meaningful testing while avoiding

unnecessary testing. It is important to note that

the increasing requirements to ensure chemical

safety generate significant costs throughout the

supply chain and these will inevitably be reflected

in the price of the final product.

10 11

>> Withouth specifiying and using the correct test method for a RSL substance test results are not reliable.

12

TFL Eco Guidelines – Information Restricted Substances

Testing for heavy metals

One commonly listed test method for heavy met-

als, EN 71-3, is a method for toys. What many do

not realise is that the extraction process is made

with a hydrochloric acid solution between pH 1.0

– 1.5, in order to simulate the conditions inside

the human stomach. These very acid conditions

are likely to extract some Cr from chrome-tanned

leather and there could be difficulty for leather to

comply with the extractable Cr limit.

For extractable heavy metals the new method,

EN ISO 17072-1, which uses a synthetic perspira-

tion solution at pH 5.5, is a much more realistic

and correct test for leather. Many brands and

Ecolabels have recognised that for clothes the

synthetic perspiration extraction method at pH

5.5 (typically written EN ISO 105-E04) corre-

sponds to the real-life situation and they use this

extraction specification.

Testing VOC emissions

The JAMA test (issued by the Japnese Automo-

tive Industry) involves sampling air from inside

a car and this is now in the process of being

formalised as an ISO Standard (ISO 12219-1). For

those involved in supplying leather and other car

interior materials, this is not a practical proce-

dure for evaluating individual items. Several test

methods for sampling air using samples in closed

bags or chambers have been developed (i.e. TSM

0508G-2009, VDA 278) as more practical ways

of analysing the emissions. At this stage there are

still variations in the temperature, humidity and

air flow between the different methods.

Test methods and specifications>> How are detection limits established?

In the following more detailed technical

information will be given on those restricted

substances relevant to leather and the related

test methods and specifications.

Chosing the right test method

Many tanners pass restricted substance lists

(which they e.g. receive from customers/brands),

together with specifications and test methods

onto their chemical suppliers, asking them to

guarantee that the chemicals comply with the

same specifications as they must meet for the

leather. That the specifications and test methods

are specifically for leather is often not under-

stood. The test methods listed in brand or

manufactuerer RSL lists are in most cases only

relevant for testing leather and not suitable for

testing chemical products. Withouth specifiying

and using the correct test method for a RSL sub-

stance test results are not reliable.

Formaldehyde testing

For example, requests to test dyes for formalde-

hyde (EN ISO 17226-2) and Cr(VI) (EN ISO 17075)

using colorimetric test methods is simply not

possible. Trying to determine the formaldehyde

content in chemicals according to EN ISO17226-1

gives wrong results, since this test method

requires an acidification to low pHs, causing the

break-down and possible release of bound formal-

dehyde from the chemical. It is correct to acidify

a water extract of the leather to determine the

formaldehyde content, but it is not correct to

acidify a chemical solution.

12 13


Test methods for leather: Leather is a com-plex matrix and the extraction must be validated between test laboratories.

Who develops test methods for leather?

Most of the restricted substance lists show the

required ISO or EN Standard to be used for making

the test. However, with the rapid increase in the

number of restricted substances, there is quite

often no international leather method available

and many simply list brief instructions like “solvent

extraction, GC-MS”. RSL lists often give the test

method used for water analysis, which ignores the

most important aspect, namely the extraction

step from leather. Leather is a complex matrix and

the extraction must be validated between test

laboratories. Some inter-lab trials have shown very

large differences caused by different extraction

procedures. Several test houses have their own

internal test procedures, but until the procedures

can be verified by inter-lab comparison trials, it is

often difficult to validate such a method. The in-

ternational ISO Standards are verified by validated

inter-lab trials to check that the test procedure

is robust and gives consistent results between

laboratories.

How are detection limits established?

The detection limits for test procedures should be

based on inter-lab trials using the best available

test procedures. Sometimes the limit is based on

several factors, such as the extraction from a diffi-

cult matrix like leather, which causes background

noise in chromatograms. Once the analytical

result variability between labs exceeds 50%, then

typically this is the detection limit for this method.

Important is that the detection limits are not es-

tablished using pure substances, since this ignores

the critical impact of the leather extraction.

Very important is that detection limits for test pro-

cedures are recognised and respected; recently

there have been 2 cases of detection limits being

reduced below what the test procedures can reli-

ably measure. For example, the 30 mg/kg limit for

aromatic amines in EN ISO 17234-1 was verified

in several inter-lab trials. The analytical technique

requires an extraction from leather and as well

a reduction reaction to cleave the azo dyes and

form the amines. The resulting complex matrix

means that the background noise and interfer-

ence from other extracted substances in the

chromatogram was the key factor in establishing

this 30 mg/kg limit. To find some restrictions now

requesting a 20 mg/kg limit with the comment

– we want to be sure we are under the 30 mg/

kg limit of the EU – ignores the scientific logic

for detection limits. Similarly, the EN ISO 17075

Standard for Cr(VI) in leather clearly explains that

3 mg/kg is the lowest reliable detection for the

procedure. However, some restrictions now list

a requirement to measure to 2 mg/kg and list

the same test method – this is not possible! It

must not be forgotten that it is not the detection

limit of the reference sample in pure solvent that

counts, but rather the detection in the leather

extraction matrix, which can be a complex mix

of side reactions and extracted materials that are

removed from the leather.

What are natural environmental limits?

All around us there are traces of various chemical

substances. Requests for exceedingly low levels of

restricted substances can very often be close to or

even below the levels found in nature. The leather

industry uses water from rivers and wells, the

chemical industry uses technical grade raw ma-

terials, so it is clear there will be natural levels for

some restricted substances. Also often overlooked

is that our natural raw material, namely the hides

and skins, will also contain natural trace levels of

restricted substances, for example, heavy metals.

Some recent requests for lead (Pb) levels in leather

of less than 0.1 ppm are probably lower than that

typically found in the natural environment.

14


>> The detection limits for test procedures should be based on inter-lab trials using the best available test procedures.

14 15


Restricted substances relevant to leather manufacture Here is listed some basic information about

each of the restricted substances that could be

relevant for leather. These substances or group

of substances are the ones typically encountered

and are not an exhaustive list of all restricted

substances. The information below is only an

overview and the individual regulations need

to be consulted for full details. To help find the

restricted substances quickly they are listed in

alphabetical order.

Listed at the end of this section are several sub-

stances and substance groups that are not rele-

vant for leather, but are still very often requested.

Acetaldehyde

Acetaldehyde recently attracted a lot of attention

by car makers particularly in the Asian automotive

market. In GB/T 27630-2011 (the Chinese Regu-

lation) limits for acetaldehyde emissions from car

leather are set to be 0.2 mg/m3 which is extreme-

ly low and far beyond any health risks. Acetalde-

hyde is not being used in the manufacture of any

leather chemical product and even if present in

trace amouts in chemical products those do not

contribute to the acetaldehyde readings. It has

to be assumed that acetaldehyde is continuously

formed by oxidation or fermatation of certain

substances (fats, sugars, etc.) but also during the

testing.

Specific TFL comment

The only way to achieve above low levels is the

use of a scavenger product. TFL has developed

the product A 3210 which can be used in wet-

end and finishing applications to suppress acetal-

dehyde formation.

Allergenic and sensitising dyes

, These dyes are typically disperse dyes, which

are used for colouring textiles. The problem oc-

curs with skin contact to the coloured material.

, Disperse dyes are not water-soluble so are

normally not used for dyeing leather.


TFL does not use any of the above types of

allergic or sensitizing dyes in their leather dye

range of: SELLA® Cool, SELLA® Derm, SELLA® Fast,

SELLA® Star, SELLAFLOR®, SELLASET®.

Aromatic amines from azo dyes

Azo dyes are some 90% of all leather and textile

dyes. Azo dyes break down under reductive con-

ditions to form aromatic amines.

, 22 aromatic amines are forbidden in the EU

Regulation 1907/2006 Annex XVII and listed in

Appendix 8. These 22 amines are known to be

carcinogens or potential carcinogens.

The EU Regulation specifies in Appendix 10 the

test method for each type of substrate and in An-

nex XVII defines the detection limit of 30 mg/kg

for each amine in leather. The official test method

for leather is CEN ISO/TS 17234; this method is

now updated and replaced by EN ISO 17234-1.

Until now Ecolabels and brands have used the EU

limit of 30 mg/kg, however;

, In 2009 China introduced a 20 mg/l limit and

some global brands have started to also specify

this limit which is lower than the EU Regulation.

, The leather extraction and chemical reaction

step gives a complex matrix and analysing at

less than 30 mg/kg can result in considerable

variations and possible wrong assignments of

amines. This was the reason for setting the limit

value at 30 mg/kg in the EU Regulation.

16

Restricted substances: These substances are the ones typically encountered and are not an exhaustive list of all restricted substances.


Careful: A small number of Ecolabels restrict

2 additional aromatic amines that are not for-

bidden. Some test houses measure the presence

of the forbidden amine, 4-aminoazobenzene,

by analysing for the 2 amines, 4-aminoaniline

(p-phenylene diamine) and aniline, both which

are not forbidden.

Depending on the reduction conditions it is

possible that for the widely used black dye, C.I.

Acid Black 210, some 4-nitroaniline is reduced to

4-aminoaniline, which can lead to test houses giv-

ing a false positive result for 4-aminoazobenzene.

The new method, EN ISO 17234-2 should be used

for testing leather for 4-aminoazobenzene.


All TFL dyes (SELLA® Cool, SELLA® Derm, SELLA®

Fast, SELLA® Star, SELLAFLOR®, SELLASET® ) do

not contain azo dyes made with the forbidden

amines. Most commercially available azo dyes do

not break down to give these forbidden amines.

Biocides

The EU Directive 98/8/EC, Biocidal Products

Directive (BPD), controls and regulates the use of

biocides, they are not part of REACH. Registration

of a biocide is very expensive and only a few ac-

tive biocide substances are expected to be avail-

able for the leather industry in the near future.

Biocides are applied to raw hides & skins

(bactericides) and in pickling/tanning (fungi-

cides) to stop the leather being damaged during

transport and storage. Some of the chlorinated

phenol type of biocides are now restricted. Only

a few fungicides dominate the leather indus-

try usage. The big 4 fungicides are commonly

known by their abbreviations, for example, PCMC

(para-chlor-meta-cresol), OIT (2-n-octylisothi-

azolin-3-one), OPP (ortho-phenylphenol), TCMTB

(2-(thiocyanomethylthio) benzothiazole).

The Ecolabel, “Der blaue Engel” (the blue angel),

gives recommendations for allowable limits in

leather of the active fungicide components:

PCMC < 300 mg/kg, OIT < 100 mg/kg,

OPP < 500 mg/kg and TCMTB < 500 mg/kg.

Biocides are also used to stabilise chemical

products that contain natural or biodegradable

substances. These can be susceptible to bacteria

or fungi attack. However, the quantity of biocide

that would then be applied to the leather with

the chemical is some 100 to 1000 times less than

is applied to protect leather in the beamhouse

process.

Biocides found often in waste water emissions

from tanneries are not only from products

used during leather manufacture but can also

derive form the animal raw hides where

pesticides etc. are being used for protecting

animals from diseases.


TFL uses biocides which comply with the EU

Biocidal Product Directive and the ‘Blue Angel‘

(Blauer Engel) issued by German Enviornmental

Ministry.

16 17

>> The international ISO Standards are verified by validated inter-lab trials.

18


Chlorinated paraffins (SCCP, short chain)

Short chained chlorinated paraffins (SCCP) are

those with a chain length of C10–C13.

EU Regulation 1907/2006 (formerly as EU

Directive 2002/45/EC) restricts the marketing

and sale of SCCP in preparations to a maximum of

1% (= 10 000 mg/kg). Analytical methods to

determine SCCP in leather are still being devel-

oped. Currently there is no validated test method

available.

Note: The medium chain MCCP (C14–C17) and

long chain LCCP (C18–C30) chlorinated paraffins

are not restricted by EU Regulation nor by the

ZDHC Leather MRSL list. The presence of MCCP

must be listed in the EU-Safety Data Sheet.

Specific TFL comment:

The international range of CORIPOL® fatliquors

from TFL comply with the EU Regulation restrict-

ing SCCP.

Chlorinated phenols (PCP, TeCP and TriCP)

Chlorinated phenols were previously used

extensively to inhibit mould growth. The 3 chloro-

phenols listed are now forbidden in consumer

products:

, PCP (pentachlorophenol)

, TeCP (tetrachlorophenol)

, TriCP (trichlorophenol)

The detection level of 5 mg/kg has become

the accepted limit using the EN ISO 17070 test

method for leather.


TFL does not use PCP, TeCP and TriCP in the TFL

range of leather chemicals.

Boron containing substances

Boric acid and disodium tetraborate, common-

ly called borax, have recently been notified as

candidates in the SVHC decision making process.

They are classified as toxic for reproduction.

These boron compounds are widely used in many

industries and if they do become SVHC substanc-

es, then their limited use in some leather industry

processes will need to be replaced.

Boric acid is used in some deliming formulations

and borax has been used in small amounts in

leather chemical formulations to adjust the pH

and penetration.


Leather made with the international range of TFL

leather chemicals would comply with the SVHC

requirements.

Brominated flame retardants

A group of polybrominated flame retardants are

restricted. They are used in plastics. (They are not

water soluble so not suitable for wet-end leather

applications).


SELLA® Tec products from TFL used for fire pro-

tection do not contain polybrominated organic

flame retardants.

18 19


Uses of Chromium: The Cr-containing chemicals used in the manufacture of leather are all based on Cr(III).

The use of the product SELLASOL® C6 in

the last step of wet-end operations helps to elim-

inate the presence of any Cr(VI) in the leather.

SELLASOL® C6 can also retard or prevent the

formation of Cr(VI) during transport or storage.

Post formation of Cr(VI) however can not be ruled

out especially if an excess amount of unsaturated

fats are present.

Dimethyl fumarate

Dimethyl fumararte is a solid, which sublimes to

a gas. It has good anti-fungal properties, so it has

been used in sachets inside the packaging for so-

fas, shoes and boots, especially those items being

exported from Asia to Europe.

Dimethyl fumarate is an allergic sensitizer at low

concentrations and can cause severe skin rashes

and irritations. Since 2009 the EU has forbid-

den the marketing of any products containing

dimethyl fumarate. It is not used as a biocide for

leather, the problem was caused by the inclusion

of dimethyl fumarate inside the packaging and it

depositing on the surface of the consumer goods.

Careful: Dimethyl fumarate is commonly referred

to as DMF in publications and the media. It should

not be mixed up with the solvent dimethyl forma-

mide that chemists have traditionally called DMF.


TFL does not use dimethyl fumarate in any of the

TFL leather chemical products.

Formaldehyde

Formaldehyde is used extensively for making

industrial chemicals. For example, in the leather

industry many syntans are formaldehyde poly-

mers. Once the formaldehyde has reacted it is

no longer present as formaldehyde. Some small

residues of unreacted formaldehyde can occur

in a few products, typically melamine resins

Chromium (VI)

The hexavalent chromium oxidation state (Cr(VI))

is allergenic and carcinogenic if inhaled and thus

restricted by the EU. The detection limit is 3 mg/

kg in the leather test method, EN ISO 17075.

This is the level generally accepted for Cr(VI) in

leather. Some Ecolabels and brands try to be one

step better and specify 1 or 2 mg/kg, but they list

the same test method. This is not correct as the

ISO Standard method includes information clearly

pointing out how the 3 mg/kg detection limit

was established. Lower detection limits cannot be

justified with this technique.

The Cr-containing chemicals used in the manufac-

ture of leather are all based on Cr(III). However,

during manufacture it is possible that traces of

Cr(VI) can be formed if certain measures in the

the application process are not properly followed.

Most important are good removal of natural

grease, avoidance of fatliquors with high content

of unsaturated fats and any oxidising agents.

Use of vegetable tannins and anti-oxidants help

to suppress the formation of Cr(VI) whereas

low humidity and high temperature can trigger

their formation particularly in the presence of

unsatured fats. Cr(VI) is one restricted substance

where, through the choice of the application

process, the tanner is responsible for avoiding its

presence.

The Cr(VI) oxidation state does not form organ-

ic complexes, so dyes based on stable organic

Cr(III)-complexes do not form Cr(VI) in the leather.

Careful: Analyses for total Cr measure all the oxi-

dation states of chromium. This technique cannot

be used to determine the Cr(VI) content.


The Cr-containing TANNESCO® syntans from TFL

contain only Cr(III) salts, no Cr(VI) is present.

20


and some cationic dye fixing agents. Different

analytical procedures are used to measure the

free unbound formaldehyde and the hydrolysable

formaldehyde (only released by interaction with

water). For leather used in automotive seats the

free formaldehyde test (emission into air) is im-

portant. For leather in shoes with skin contact the

water extraction method determines the free and

hydrolysable formaldehyde.

There is currently no EU regulation restricting

the use of formaldehyde in leather.

, Japan and China have restrictions for articles,

especially those in skin contact

, Ecolabels and brands set formaldehyde limits,

e.g. as 20mg/kg (20 ppm) for children and

75mg/kg (75 ppm) for adult shoes

, The automotive industry has limits for

formaldehyde in the leather (often 10 ppm)

and for emissions into the cabin air

Careful: Select the correct analytical methods

for leather:

, Water extraction (EN ISO 17226-1) –

measures free and hydrolysable formaldehyde

, Emission into air (EN ISO 17226-3) –

measures free formaldehyde


The SELLATAN® and SELLASOL® syntan prod-

ucts are either low formaldehyde or formalde-

hyde-free (for both the free and hydrolysable

formaldehyde). Trace levels are listed in separate

TFL Statement of restricted substances. With

suitable application processes, leather can be

prepared to comply with the very low residual

formaldehyde requirements given above.

For example, by using a syntan like SELLATAN®

WL-W and the auxiliary syntans SELLASOL® HFN,

SELLASOL® FTF or SELLASOL® MI, it is possible to

make leathers that are free of residual formalde-

hyde. The MAGNOPAL® polymer retanning agents

are free of formaldehyde.

Heavy metals

EU limits for heavy metals in consumer items have

been introduced via the EN Standard for extract-

able heavy metals in toys. In the USA the CPSC

sets levels for heavy metals in consumer items.

The EN 71-3 method has defined the following

maximum limits for extractable heavy metals:

As: 25 ppm, Cd: 75 ppm, Total Cr: 60 ppm,

Hg: 60 ppm, Pb: 90 ppm, Sb: 60 ppm,

Ba: 1000 ppm, Se: 500 ppm. The low pH

extraction process could make it difficult for

chrome-tanned leather to comply. Ecolabel limits

for heavy metals are often much lower and nor-

mally they also specify total metal. For example,

some textile Ecolabels set very low limits for total

Cr. Obviously achieving these lower levels is not

possible with Cr-tanned leather.

Other Ecolabels, such as the SG Label, accept

chrome-tanned leather and restrict only the

extractable Cr and Cr(VI).

Careful: Check if the specification is for extract-

able or total metal content and check which

extracting agent is specified!

, The extraction is at pH 1–1.5 for the EN 71-3

method for toys

, Ecolabels often specify extraction

with a pH 5.5 synthetic perspiration solution

(prepared according to ISO 105-E04)

Often there are requests from certain brands for

metal-free leather. Such request should be speci-

fied for ‘free of toxic heavy metals’ since presence

of non-toxic metals can be critical to achieve

certain performances (e.g. high light fastness of

metal dyes. Metal-free leather according to EU

guidline is specified as as containing less than

0.1 % of Cr(III), Al, Ti, Zr, Fe.

20 21

and leather industry. In Europe they have now

been replaced by alternative surfactants.

In order to show NPEO containing preparations

have not been used, Ecolabels can require less

than 100 mg/kg in leather.


The TFL international range of BORRON® surfac-

tants are not based on nonylphenol ethoxylate.

Organotin compounds

TBT (tributyl tin), DBT (dibutyl tin) and MBT (mo-

no-butyl tin) are restricted chemicals. These are

used as antimicrobals, e.g. in paints for boats.

Tin compounds can be used as catalysts in the

production of PU polymers. Trace levels of or-

ganotin compounds may be present in PU finishes

but after application they will be fixed.


TFL does not add restricted organotin compounds

to any leather chemical product.

Perfluorochemicals (PFC)

The fluorochemicals based on C8 chemistry, eg.

PFOS (perfluorooctane sulfonate) has been found

to be persistent in nature so it has been forbid-

den. The EU Regulation limits PFOS to 0.005 % by

mass in consumer goods. Analytical methods are

complicated and an ISO method still in devel-

opment.The corresponding acid form, PFOA, is

usually also restricted by brands and Ecolabels.

The same applies for chemicals based on C6 Fluor

Chemistry. Fluorochemical products based on C4

chemistry have by far the lowest degree of bioac-

cumulation and toxicity among all fluorochemical

products. Nevertheless some of the brands have

decided to completely restrict the use of PFC.

Specific TFL comments:

Other than Cr(III), TFL is not adding the above

heavy metals (As, Cd, Cr, Hg, Pb, Sb, Ba, Se) to

any TFL product. Metal content of TFL dyes and

pigments are listed in separate TFL Statement of

Restricted Substances.

Some dyes are organic metal complexes of either

Cr(III), Co, Cu or Fe. This information is listed in

section 12 of the TFL Safety Data Sheet. The TFL

dyes and pigments also comply with the stringent

ETAD guidelines for heavy metals.

N-methyl pyrrolidone

N-methyl pyrrolidone (NMP) has been extensively

used as a high boiling point solvent and flow-im-

prover in finishing formulations. In the Californian

Proposition 65 legislation, NMP was classified as

toxic for reproduction. In the EU, the classifica-

tion has now been changed to toxic for repro-

duction and from the end of 2010 any product

formulation containing quantities of NMP above

0.1% must list this in the Safety Data Sheet. Most

brands and automotive manufacturers now do

not allow the use of NMP in finishing products.


No product in TFL range uses NMP and NEP

(N-ethylpyrrolidone).

Nonylphenol ethoxylate and nonylphenol

The EU Regulation requires that nonylphenol (NP)

and nonylphenol ethoxylate (NPE or NPEO) are

not to be used in preparations at levels greater

than 0.1% during leather (or textile) processing if

the waste water is discharged. The generalised

form of these type of substances is written as

APEO (alkylphenol ethoxylate). Until recently the

nonylphenol ethoxylates were used extensively as

non-ionic surfactants and emulsifiers in the textile


22


TFL does not have PFOS or PFOA in the fluo-

rochemical products it supplies. TFL fluoro-

chemical products are all based on C4 chemistry.

Phenol

Some RSL lists regulate the content of free phe-

nol. Phenol is used in the manufacture of poly-

mers (synthetic tanning agents) and as in the case

of formaldehyde trace amounts can be found in

some of these products.


Some TFL products from SELLATAN®, SELLASOL®

range contain traces of free phenol resulting from

the polymerisation process. Trace level amounts

are listed in the separate TFL Statement of Re-

stricted Substances.

Phthalates

6 phthalates (DINP, DEHP, DNOP, DIDP, BBP and

DBP) are restricted in the EU. These are used as

softening agents in plastics to give it the required

flexibility. The EU Regulation limits individual

phthalates to 0,1% (= 1000 mg/kg) in chemical

preparations.

Ecolabels and leather shoe manufacturers typi-

cally set limits of < 500 mg/kg total phthalates in

leather.


TFL does not use the restricted phthalates in the

leather chemical products.

Polycyclic aromatic hydrocarbons (PAH)

Polycyclic aromatic hydrocarbons (PAH) are

present in tar oils. These typically dark coloured

extracts are used as cheap softening agents

in rubber and some plastics. It is most unlikely

that they would be used by the leather industry.

Naphtalene, the most simple PAH substance, is

not intentionally used in leather manufacture but

present in trace level in some dispersing products.


TFL does not use PAH substances intentionally in

leather chemical products. Naphtalene can, how-

ever, be found in trace levels in some dispersing

agents. Levels are listed in separate TFL statement

for Restricted Substances and do not exceed any

allowable limits of major RSL and MRSL.

Substances of Very High Concern (SVHC)

Substances of Very High Concern (SVHC) are an

important new part of the REACH Regulation

(EU 1907/2006) in the EU. After a consultancy

process and risk evaluation, those substances that

are considered to be SVHC will be listed in Annex

XIV of the EU Regulation. Currently there are

168 chemical substances in the SVHC candidate

list, but at present none have yet been assigned

SVHC status in Annex XIV which would then mean

that substances could not be generally used and

need authorisation for a particular use. Each EU

member country can introduce substances (with

supporting documentation) for the candidate

list. After this, the candidate substances undergo

a risk assessment process before the decision

is made about becoming a SVHC substance in

Annex XIV. The risk assessment evaluation is an

important step in judging the potential harm of

chemical substances.

The EU Regulation requires that special efforts

should be made to replace the use of any Annex

XIV listed SVHC substances.

Consumer articles, e.g. leather, containing more

than 0.1 % of a SVHC substance will not be allowed

to be imported into the EU region. Presence of a

SVCH substance in chemcials products at levels

higher than 0.1 % needs to be declared and user


22 23

needs to be informed by the chemicals supplier

on its safe use. The current 168 candidate SVHC

substances, except for the recently announced

boric acid and disodium tetraborate, are not likely

to be used by today’s leather industry.


As soon as a chemical substance is put on the

candidate list many brands and Ecolabels react

immediately restricting the use of the candidate

substance. From a legal point of view, candidate

chemicals can still be used and in many cases the

residual amount in leather may not exceed 0.1 %.

In the manufacture of active TFL sales products

no SVHC substance is being used.

Volatile Organic Compounds (VOC)

Volatile Organic Compounds (VOC) refer to

organic solvents, especially those with a boiling

point between 50°C – 260°C. If present, these

organic substances can be emitted into the

air during leather production, especially in the

finishing process. The EU regulates the amount of

VOC output that can be emitted into the air with

respect to leather manufacture. The automotive

and upholstery industries place restrictions on

the VOC emission from leather. Both industries

have different test methods and requirements.

The VOC is measured by heating the leather in a

closed chamber and the individual emitted VOC

substances are determined by a mass spectrom-

eter( i.e VDA 278 test method ) The results can

be influenced by the time since the leather was

made and the storage method. The Very Vola-

tile Organic Compounds (VVOC) are those with

a boiling point below 50°C. The semi-volatile

organic compounds (SVOC) have boiling points

between 260°C – 400°C.

VOC emissions of special interest coming from

leather are formaldehyde, acetaldehyde, ben-

zene, toluene, xylene, ethylbenzene, styrene,

acrolein, NMP and NEP and these are all including

various RSL and regulations.


By using TFL products it is possible to comply with

the total VOC emission requirements for above

mentioned substances set by brands, Ecolabels

and OEM’s.

Restricted substances not relevant

to the leather industry

Some tanneries give to their chemical suppliers

long lists of restricted substances that they have

received from their customers. Many of the listed

substances have effectively no relevance for the

leather industry of today. For many of them the

only reason for listing seems to be for complete-

ness and perhaps to make additional tests.

Typical non-relevant substances for leather are

asbestos and blue colorant.

The EU Regulation 1907/2006 (formerly in EU

Directive 2003/03/EC) bans the use of a “blue

colorant”, Index No. 611-070-00-2. According to

current knowledge this forbidden blue colorant

has never been sold to the worldwide leather

industry. No samples of the dye have been able to

be located so it is not possible to analyse for this

colorant.

, Chlorofluorocarbons (CFC) and

hydrochlorofluoro-carbons (HCFC)

, Heavy metals: arsenic (As), beryllium (Be),

bismuth (Bi), cadmium (Cd), mercury (Hg),

selenium (Se)

, Nickel metal

, Pesticides

, Polychlorinated biphenyls (PCB) and

terphenyls (PCT)

, Polyvinyl chloride (PVC)


24

ARACIT®

Preserving agents for the short-term preservation

of fresh hides and for soaking.

BORRON®

A range of surfactants and degreasing agents,

as well as sequestering agents. High efficiency,

tailor-made products for all process steps.

CORIPOL®

A range of fatliquoring agents based on natural

and synthetic fatty substances.

RODA®

The TFL range of products suitable for use in the

finishing of leather in all types of manufacturing

processes.

SELLA® Cool

A range of selected dyes that comply with the TFL

Cool System requirements. They do not absorb

radiation in the near-infrared, which restricts the

rise of temperature on the leather surface when it

is exposed to sunlight.

SELLA® Derm

A range of concentrated solutions of homoge-

neous, salt-free, mainly metal complex dyes in

water-miscible and environmentally acceptable

organic solvents.

SELLA® Fast

A large range of acid and direct dyes for the

coloration of leather where good levelness,

covering power, brilliance, shade consistency and

good Fastness properties are required.

SELLA® Star

A compact range of special acid dye mixtures to

produce various brown, beige and olive shades,

featuring good general Fastness properties.

SELLA® Tec

A group of leather chemical products suitable

for manufacturing flame retardant leather.

SELLASET®

A range of 1:2 metal complex acid dyes especially

suitable for trichromatic dyeing systems.

SELLASOL®

A range of auxiliary syntans for the retanning

of leather.

Glossary>>

24 25

Considering the many possible substances of concern, one may ask how safe leather really is and

how safely it can be made?

The simple answer is: Leather made with state-of-the-art technology and chemicals is a very safe

product. It is possible to manufacture leathers that comply with the most stringent requirements as to

restricted substances and no health risks can be associated with such leather, which is formed from

a natural product.

This requires that manufacturers take care to select the appropriate processing chemicals and

apply them correctly. TFL has been pioneering the area of ecological leather manufacturing through

the development of various innovative product technologies. One example of them is the

TFL White Line Technology which complies with the very stringent SG Label standards. White Line

leathers have been tested by dermatologists on highly sensitive test persons and found not to cause

any allergenic reaction.

Is leather a save product?>> Are there any final concerns?

26

>> Our products all comply with highest standards regarding hazardous substances and environment sound production.

26 27

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